The use of X‐ray absorption spectroscopy for monitoring the thickness of antiwear films from ZDDP

X‐ray absorption near edge structure (XANES) spectroscopy at the P K‐edge was used to monitor ZDDP antiwear film thickness with rubbing time. Thermal immersion films of varying thickness were generated from the ZDDP and analysed using XANES spectroscopy and the particle induced X‐ray emission (PIXE) technique. P K‐edge XANES edge jumps and (1s → np) peak heights of the spectra were plotted against PIXE mass thickness values in order to establish calibration curves. Antiwear films were analysed using XANES spectroscopy, and average mass thicknesses were extrapolated from the calibration curves. A set of antiwear films formed in the presence of ZDDP and then further rubbed in base oil (no ZDDP) showed no significant decrease in film thickness. A set of antiwear films rubbed in the presence of ZDDP for various lengths of time showed an increase in film thickness, followed by thinning of the film. The decrease in film thickness is believed to be due to wear caused by the ZDDP solution decomposition products acting as an abrasive in the contact region. This revised version was published online in July 2006 with corrections to the Cover Date.     

Molecular structure and driving force to metastable states: Janus faces in polymer crystallization

This paper is a retrospective of a past dedicated to research on polymers and a situation sketch of the present and the near future. (Co)polymers discussed are mainly based on ethylene. (Cross‐)fractionation techniques combined with state‐of‐the‐art characterization techniques, like quantitative differential scanning calorimetry, are powerful tools for the study of the links between two main topics: molecular structure and crystallization/melting. These form the two ‘Janus faces’ polymers can show, namely Face 1: the molecular structure resulting from polymerization with the keyword ‘nature’; and Face 2: the driving force of crystallization towards a metastable state, with the keyword ‘nurture’. After all, to meet demands for properties of products, in principle one starts with a given molecular architecture, after which dedicated processing, including application of temperature–time ramps, has to do the job. With new instrumentation, especially fast scanning (chip) calorimetry, for the first time in history the driving force towards crystallization into one of the possible metastable states – via Face 2 – can be controlled, of course within certain limits given by Face 1. This promising outlook of combining the faces to a useful symbiosis of Janus will be a challenge for those working in the science of crystallization of polymers. © 2018 Society of Chemical Industry     

Theoretical and Experimental Investigation of Gas-Lubricated,Pivoted-Pad Journal Bearings

This paper presents some of the theoretical predictions and experimental results for the steady-state characteristics of a gas-lubricated, pivoted-pad journal bearing of finite length. An analytical expression for the prediction of load-carrying capacity for these bearings is developed from numerical computer solutions. Sample calculations are presented to show how the theoretical data may be utilized in the design of an actual pivoted-pad bearing. Improvements over previous approximate theories are discussed.     

The effect of humidity and oxygen partial pressure on degradation of Pt/C catalyst in PEM fuel cell

Durability of Pt/C oxygen reduction reaction (ORR) catalyst remains one of the primary limitations for practical application of proton exchange membrane (PEM) fuel cells. In this work, the effects of relative humidity and oxygen partial pressure on platinum catalyst degradation were explored under potential cycling. At 60 °C, the loss rates of Pt mass and catalyst active surface area were reduced by about three and two times respectively when the relative humidity was lowered from 100% to 50%. The effects of oxygen partial pressure on cathode degradation were found to be insignificant. Cyclic voltammetry studies showed a slight increase in Pt electrochemical oxidation by water when the humidity increased from 50% RH to 100% RH. The rates of Pt dissolution were only slightly affected by change in humidity, and the accelerated catalyst degradation was ascribed to the increased Pt ion transport in the more abundant and larger water channel networks within the polymer electrolyte. Based on the parametric study results from our previous cathode degradation model, it was estimated that the diffusivity of Pt ions at fully humidified conditions was three times that of the value at 50% RH and 60 °C.     

Relative dominance of physical versus chemical effects on the transport of adhesion-deficient bacteria in intact cores from South Oyster, Virginia

Bacterial transport experiments were conducted using intact sediment cores collected from sites on the Delmarva Peninsula near South Oyster, VA, to delineate the relative importance of physical and chemical heterogeneity in controlling transport of an adhesion-deficient bacterial strain. Electron microscopy revealed that the sediments consisted of quartz and feldspar with a variable amount of clay and iron and aluminum hydroxide coatings on the grains. A nonmotile, gram-negative indigenous groundwater strain, designated as Comamonas sp. DA001, was injected into the cores along with a conservative tracer bromide (Br). DA001 cells were 1.2 x 0.6 microm in size with a hydrophilic surface and a slightly negative surface charge. Bacterial breakthrough preceded that of Br. This differential advection phenomenon can be accounted for by reduction of the effective porosity for the bacteria relative to Br. The distribution of cells remaining in the core as determined by scintillation counting and phosphor imaging techniques was variable, ranging from nearly uniform concentrations throughout the core to exponentially decreasing concentrations with distance from the point of injection. The fraction of bacterial retention in the core was positively correlated with the abundance of the metal hydroxides and negatively correlated with grain size. Because grain size was inversely correlated with the abundance of the metal hydroxide coatings, it was necessary to separate the effects of grain size and mineralogy. The fraction of the bacterial retention accounting for the effect of grain size, the collision efficiency, exhibited no correlation with the abundance of the metal hydroxides, indicating that the bacterial retention was primarily controlled by grain size. Reasons for the lack of influence of mineralogy on bacterial transport include (i) the slightly negatively charged bacterial surfaces; (ii) an insufficient heterogeneity of sediment surface properties; and (iii) the masking of the positive charge of the metal hydroxide surfaces by adsorbed organic carbon (up to 1180 ppm). This study demonstrates that the laboratory-based bacterial transport experiments are effective in delineating physical versus chemical controlling factors and provide an important link to field-based bacterial transport studies.